U.S. patent number 4,866,190 [Application Number 07/152,029] was granted by the patent office on 1989-09-12 for process for the preparation of perhaloalkanesulfinic and -sulfonic acids, perhaloalkanesulfinic and -sulfonic acid salts and other derivatives of these acids.
This patent grant is currently assigned to Rhone-Poulenc Chimie. Invention is credited to Bernard Langlois, Marc Tordeux, Claude Wakselman.
United States Patent |
4,866,190 |
Tordeux , et al. |
September 12, 1989 |
Process for the preparation of perhaloalkanesulfinic and -sulfonic
acids, perhaloalkanesulfinic and -sulfonic acid salts and other
derivatives of these acids
Abstract
A process for the preparation of perhaloalkanesulfinic and
-sulfonic acids and derivatives of these acids. A
perhaloalkanesulfinic acid salt is prepared by contacting a metal
hydroxymethanesulfinate (preferably, a sodium, zinc or copper
hydroxymethanesulfinate) with a perhaloalkyl halide group, in a
polar solvent. Optionally, the perhaloalkanesulfinic acid salt is
then converted to a perhaloalkanesulfinic or -sulfonic acid or a
derivative of either of these acids.
Inventors: |
Tordeux; Marc (Sceaux,
FR), Langlois; Bernard (Lyons, FR),
Wakselman; Claude (Paris, FR) |
Assignee: |
Rhone-Poulenc Chimie
(Courbevoie, FR)
|
Family
ID: |
9347674 |
Appl.
No.: |
07/152,029 |
Filed: |
February 3, 1988 |
Foreign Application Priority Data
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|
|
|
|
Feb 4, 1987 [FR] |
|
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87 01503 |
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Current U.S.
Class: |
556/111; 556/119;
562/113; 562/125; 562/829; 562/834 |
Current CPC
Class: |
C07C
313/04 (20130101); C07C 309/00 (20130101) |
Current International
Class: |
C07C
303/32 (20060101); C07C 303/00 (20060101); C07F
1/08 (20060101); C07F 1/00 (20060101); C07F
3/06 (20060101); C07F 3/00 (20060101); C07C
309/00 (20060101); C07C 309/06 (20060101); C07C
313/00 (20060101); C07C 313/02 (20060101); C07C
145/00 (); C07F 001/08 (); C07F 003/06 () |
Field of
Search: |
;260/513.7,513F
;556/111,119 |
References Cited
[Referenced By]
U.S. Patent Documents
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|
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2732398 |
January 1956 |
Brice et al. |
4221734 |
September 1980 |
Commeyras et al. |
|
Foreign Patent Documents
Primary Examiner: Chan; Nicky
Attorney, Agent or Firm: Finnegan, Henderson, Farabow,
Garrett & Dunner
Claims
We claim:
1. A process for the preparation of a perhaloalkanesulfinic acid
salt of formula (I):
wherein R.sub.f represents a polyfluorinated perhaloalkyl group
containing at least two carbon atoms and not containing a halogen
atom other than fluorine on the carbon atom adjacent to that which
carries the SO.sub.2 group, M represents a metal, and n is equal to
1 or 2 depending on the valency state of the metal M, comprising
the step of contacting a metal hydroxymethanesulfinate of formula
(II):
wherein M and n have the same meaning as in formula (I), in a polar
solvent, with a perhaloalkyl halide of formula: R.sub.f X wherein
R.sub.f represents a polyfluorinated perhaloalkyl group containing
at least two carbon atoms and not containing a halogen atom other
than fluorine on the carbon atom adjacent to that which carries the
group X, wherein X represents chlorine, bromine or iodine, for a
time sufficient to obtain said perhaloalkanesulfinic acid salt of
formula (I).
2. The process of claim 1, wherein said metal
hydroxymethanesulfinate of formula (II) is selected from sodium,
zinc and copper hydroxymethanesulfinates.
3. The process of claim 1, wherein said polar solvent is
dimethylformamide.
4. The process of claim 1, wherein said perhaloalkyl halide of
formula R.sub.f X is a perfluoroalkyl iodide.
5. The process of claim 4, wherein said perfluoroalkyl iodide
contains from 2 to 12 carbon atoms.
6. The process of claim 1, wherein the reaction temperature ranges
from 0.degree. to 85.degree. C.
7. The process of claim 6, wherein said reaction temperature ranges
from 20.degree. to 40.degree. C.
8. The process of claim 1, wherein said metal
hydroxymethanesulfinate is an alkali metal hydroxymethanesulfinate.
Description
FIELD OF THE INVENTION
The present invention relates to a process for the preparation of
perhaloalkanesulfinic and -sulfonic acids and their derivatives.
More particularly, it relates to the preparation of
perfluoroalkanesulfinic and -sulfonic acid salts.
BACKGROUND OF THE INVENTION
Perfluoroalkanesulfonic acids are employed as wetting agents or as
surfactants in detergents. They also find utility in the
preparation of products having interfacial properties.
The preparation of these compounds by electrofluorination (for
example, according to U.S. Pat. No. 2,732,398) is known. A
preparation process employing an electrochemical method is ruled
out, however, because of its excessively high industrial cost.
Known chemical methods of preparation of these compounds involve
the condensation of sulfur dioxide with perfluoroalkylmagnesium
derivatives or with perfluoroalkyl halides in the presence of zinc
(U.S. Pat. No. 4,221,734). From an industrial safety standpoint,
such magnesium-containing derivatives, being far too violent,
cannot be used.
Zinc, moreover, disadvantageously gives rise to zinc hydroxide when
the reaction medium is treated. The separation of zinc hydroxide on
an industrial scale presents serious problems.
DESCRIPTION OF THE INVENTION
A new process has been discovered which enables the disadvantages
of the prior art to be overcome, and which is particularly
economically advantageous from an industrial standpoint.
The subject of the present invention, which has enabled these
objectives to be achieved, is a process for the preparation of a
perhaloalkanesulfinic acid salt of formula (I):
wherein R.sub.f represents a polyfluorinated perhaloalkyl group
containing at least two carbon atoms and not containing a halogen
atom other than fluorine on the carbon atom adjacent to that which
carries the SO.sub.2 group, M represents a metal, and n is equal to
1 or 2 depending on the valency state of the metal M, comprising
the step of contacting a metal hydroxymethanesulfinate of formula
(II):
wherein M and n have the same meaning as in formula (I), in a polar
solvent, with a perhaloalkyl halide of formula: R.sub.f X wherein
R.sub.f represents a polyfluorinated perhaloalkyl group containing
at least two carbon atoms and not containing a halogen atom other
than fluorine on the carbon atom adjacent to that which carries the
group X, wherein X represents chlorine, bromine or iodine, for a
time sufficient to obtain said perhaloalkanesulfinic acid salt of
formula (I). Use of alkali metal hydroxymethanesulfinates is
particularly preferred.
The present invention also provides a process for the preparation
of a compound selected from the group consisting of a
perhaloalkanesulfinic acid, a perhaloalkanesulfonic acid, and a
derivative of either of said acids, said compound being converted
from a perhaloalkanesulfinic acid salt of formula (I):
wherein R.sub.f represents a polyfluorinated perhaloalkyl group
containing at least two carbon atoms and not containing a halogen
atom other than fluorine on the carbon atom adjacent to that which
carries the SO.sub.2 group, M represents a metal, and n is equal to
1 or 2 depending on the valency state of the metal M, comprising
the steps of:
(a) contacting a metal hydroxymethanesulfinate of formula (II):
wherein M and n have the same meaning as in formula (I), in a polar
solvent, with a perhaloalkyl halide of formula: R.sub.f X wherein
R.sub.f represents a polyfluorinated perhaloalkyl group containing
at least two carbon atoms and not containing a halogen atom other
than fluorine on the carbon atom adjacent to that which carries the
group X, wherein X represents chlorine, bromine or iodine, for a
time sufficient to obtain said perhaloalkanesulfinic acid salt of
formula (I); and
(b) converting said perhaloalkanesulfinic acid salt of formula (I)
to said compound.
In contrast to the prior art mentioned above, and especially in
contrast to U.S. Pat. No. 4,221,734, in accordance with the
preocess of the present invention, the acids and derivatives of the
present invention may be prepared in the substantial absence of a
metal catalyst.
Examples of compounds of formula (I) include sodium and potassium
salts of perfluorooctanesulfinic acid, pentafluoroethanesulfinic
acid, perfluorohexanesulfinic acid and
1,1-dichloro-2,2-2-trifluoroethanesulfinic acid.
Examples of preferred polar solvents include amides such as, in
particular, formamide, dimethylformamide, N-methylpyrrolidone and
dimethylacetamide, and solvents such as sulfolane. The use of
dimethylformamide is particularly preferred.
Examples of metal hydroxymethanesulfinates include, in particular,
sodium hydroxymethanesulfinate, sold under the trade name
Rongalite.RTM., zinc hydroxymethanesulfinate, sold under the trade
name Decroline.RTM. and copper hydroxymethanesulfinate.
Examples of particularly preferred polyfluorinated perhaloalkyl
halides of the formula R.sub.f X include those containing 2 to 12
carbon atoms.
Among the class of perfluoroalkyl halides, the use of
perfluoroalkyl iodides is preferred. Indeed, these compounds are
well known for their chemical inertness, and it is particularly
surprising that in the presence of hydroxymethanesulfinates they
react to form perfluoroalkanesulfinic acid salts.
According to a preferred process for implementing the invention,
the metal hydroxymethanesulfinate, particularly an alkali metal
hydroxymethanesulfinate, is introduced into the reactor. It is
preferable to remove any oxygen present in the reactor, and then to
introduce the polyfluorinated perhaloalkyl halide. When the
reaction is complete, the reaction solvent or solvents is (are)
removed, and the sulfinic acid salt obtained is purified by
extraction with solvents such as ethyl acetate.
Derivatives of the sulfinic acid salt may be obtained by methods
well-known in the art. For example, the sulfinic acid salt may be
converted by oxidation into a sulfonic acid salt in a manner known
to the person skilled in the art (for example, by oxidation with
oxygenated water). A sulfonic acid may then be obtained, for
example, by acidifying the salt with anhydrous sulfuric acid in a
manner which is also known to the person skilled in the art. The
sulfinic acid salt itself may also be converted directly to a
sulfinic acid by such an acidification process.
An oxidation process may be carried out directly by introducing
chlorine into the reaction medium containing the sulfinic acid
salt, which enables sulfonyl chloride to be obtained.
By methods well-known to those in the art, sulfones may also be
obtained from the perhaloalkanesulfinic acid salts of formula (I)
of the invention.
It is preferable to work at a reaction temperature ranging from
0.degree. to 85.degree. C. and, more preferably still, at a
temperature ranging from 20.degree. to 40.degree. C.
The reactor preferably does not consist of a reactive material
(such as those described in the patent application published under
EP No. 165,135). The use of a glass reactor is thus preferred.
The perhaloalkanesulfonic acids and their derivatives obtained by
the process of the present invention may be employed as catalysts
in processes such as alkylation, or as surfactants, especially in
detergents.
The following examples illustrate certain embodiments of the
invention and should not be regarded as limiting the scope or
spirit of the invention.
EXAMPLE 1
PREPARATION OF SODIUM
1,1-DICHLORO-2,2,2-TRIFLUOROETHANESULFINATE
10 ml of dimethylformamide, 3.7 g of sodium hydroxymethanesulfinate
and 3.74 g of 1,1,1-trichloro-2,2,2-trifluoroethane were placed in
an Erlenmeyer flask. The mixture was stirred for 12 hrs. The degree
of conversion into sodium
1,1-dichloro-2,2,2-trifluoroethanesulfinate (.delta..sub.F =-71
ppm) was 30% relative to the trichlorotrifluoroethane and 15%
relative to the sodium hydroxymethanesulfinate.
EXAMPLE 2
PREPARATION OF PERFLUOROBUTANESULFONYL CHLORIDE
10 ml of dimethylformamide, 2.6 g of sodium hydroxymethanesulfinate
and 3.5 g of perfluorobutyl iodide were placed in an Erlenmeyer
flask. The mixture was stirred for 12 hours. By .sup.19 F NMR, it
was observed that 66% of the iodide was converted. After filtering,
the dimethylformamide was evaporated under vacuum. 20 ml of water
were added. The solids were removed by filtration. 1 liter of
chlorine was passed through the solution. 1.7 g of
perfluorobutanesulfonyl chloride were obtained by decantation.
Yield: 53% [82% yield relative to the perfluoroalkyl iodide
converted (.delta..sub.F =-104.6 ppm; b.p.=100.degree. C.), yield
relative to the sodium hydroxymethanesulfinate: 26%].
EXAMPLE 3
PREPARATION OF PERFLUOROOCTANESULFONYL CHLORIDE
(a) Example 2 was repeated, replacing the perfluorobutyl iodide
with 5.5 g of perfluorooctyl iodide. 75% of the iodide was
converted. After chlorination, 3.2 g of perfluorooctanesulfonyl
chloride were obtained. Yield: 62% (82% relative to the
perfluorooctyl iodide converted). .delta..sub.F =-104.6 ppm;
m.p.=36.degree. C.; b.p. 22 mm Hg=102.degree. C.
(b) The above experiment was repeated with 3.9 g of zinc
hydroxymethanesulfinate. In this case, the perfluorooctyl iodide
was completely converted. After chlorination, the yield was 85%,
and 42% relative to the zinc hydroxymethanesulfinate.
EXAMPLE 4
PREPARATION OF PERFLUOROOCTANESULFONYL CHLORIDE
10 ml of dimethylformamide, 3.7 g of sodium hydroxymethanesulfinate
and 5.5 g of perfluorooctyl iodide were placed in an Erlenmeyer
flask. The mixture was stirred for 12 hours. By fluorine nuclear
magnetic resonance spectroscopy, it was observed that 81% of the
iodide was converted, 24% of which was 1-hydridoperfluorooctane,
C.sub.8 F.sub.17 H. 5 ml of water were added. Dimethylformamide was
extracted with methylene chloride. 1 liter of chlorine was passed
through the aqueous solution, and 2.5 g of perfluorooctanesulfonyl
chloride were obtained. Yield: 48% (59% relative to the
perfluorooctyl iodide converted) and 24% relative to the sodium
hydroxymethanesulfinate.
* * * * *